Electronic and nuclear dynamics in molecular systems

195 Pages·2011·4.321 MB·English

by  Y Fujimura, Hirofumi Sakai

Yuichi Fujimura
Hirofumi Sakai
Electronic an
Nuclear Dynamic
Molecular Systems
World Scientific

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ELECTRONIC AND NUCLEAR DYNAMICS IN MOLECULAR SYSTEMS
Copyright © 2011 by World Scientific Publishing Co. Pte. Ltd.
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ISBN-13 978-981-283-722-6
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Printed in Singapore.
Sanjeed - Electronic and Nuclear Dynamics.pmd1 5/18/2011, 10:12 AM
April7,2011 16:3 9.75inx6.5in b1101-fm ElectronicandNuclearDynamicsinMolecularSystems
Preface
Electronic and nuclear dynamics in molecular systems play a fundamental role
in natural science and material science. The research targets are both physical
and chemical phenomena occurring in simple diatomic molecules to complex
biomolecularsystems.Inthismonograph,wefocusespeciallyonquantumdynamic
behaviorsofmolecularsystemsinwhichelectronicand/ornuclearmotionsdriven
by laser pulses are treated quantum mechanically. In the 1980’s to 2000, nuclear
quantumdynamicsinmoleculeswasextensivelyinvestigatedbymanyresearchers
includingtheNobelPrizewinnerAhmedZewail,thepioneeroffemtosecondchem-
istry. One of the greatest achievements in nuclear quantum dynamics is real-time
observationoftransitionstatesinthecourseofchemicalreactions.Thiswasmade
possible by the use of ultra-short pulses in femtosecond time regimes and their
detection system.This is now called “femtosecond chemistry”. In the first decade
of the twenty-first century, there have been further developments in laser science
and technology: pulse-shaping technique, control of carrier-envelope phase and
attosecondpulsegeneration.Thesedevelopmentshavemadeitpossibletodirectly
observeandcontrolmotionsofelectronsinmolecules,althoughthemoleculesare
restrictedtosimplemoleculesatthepresenttime.Theresultshaveprovidedfunda-
mentalideasforrealizationoffunctionaldevicessuchasultrafastswitchingdevices
andquantumcomputers.Therefore,itistimelytooverviewrecentdevelopmentsin
electronic and nuclear quantum dynamics of molecular systems from both experi-
mentalandtheoreticalpointsofview.
The purpose of this monograph is not only to review quantum dynamical
behaviorsofelectronsandnucleiofmolecularsystemsbutalsotointroduceexper-
imental and theoretical methods for graduate students and/or beginners who have
becomeinterestedinthisfield.Gapsbetweenthelevelsofbeginnersandresearchers
havebecomelargerandlarger.Theauthorshopethatthismonographwillcontribute
tobridgingthosegaps.
Thismonographisorganizedintotwopartsandeightchapters;inthefirstpart,
i.e.,Chap.1,fundamentalconceptsandprinciplesofcoherentdynamicsofelectrons
v
April7,2011 16:3 9.75inx6.5in b1101-fm ElectronicandNuclearDynamicsinMolecularSystems
vi ElectronicandNuclearDynamicsinMolecularSystems
and nuclei are described. These include wavepackets, adiabatic and nonadiabatic
treatments, quantum optimal control, and multiphoton vs. tunneling ionization. In
Chap.2,theexperimentalapparatusandmethodsformeasuringultrafastdynamics
arepresented.
In the second part, Chaps. 3 to 8, the results of experimental and theoretical
studiesonelectronicandnuclearcoherentmotionsarepresented.Methodsfortime
evolutionofelectronicandnuclearwavepacketscreatedbylaserpulsesaredescribed
in Chap. 3. Typical numerical methods are given for solving the time-dependent
Schrödingerequationofmolecularsystems.Here,thesemi-classicaltreatmentfor
interactionsbetweenmoleculesandlasersisadoptedonthebasisoftheassumption
thatquantumbehaviorssuchasspontaneousemissioncanbeneglected.Chapter4
outlines experimental setups and techniques for molecular alignment and orien-
tation with laser technologies first. Then, various applications with a sample of
alignedororientedmoleculesarereviewedtoprovetheirusefulness.Alignmentand
orientation of molecules are essential processes for the studies of selective chem-
istry under the conditions of vapor and condensed phases. In Chap. 5 theoretical
treatments of electronic and nuclear dynamics in intense laser fields are shown.
The correlated motion between the electronic and nuclei in a hydrogen molecular
ionispresented.Interelectroniccorrelationsinthesimplesttwo-electronsystem,a
hydrogenmolecule,areshown.Nonlineardynamics,Coulombexplosion,multiple
ionizationanddecompositionoffullerenesinducedbyintenselaserpulsesarepre-
sented from both experimental and theoretical points of view. Chapter 6 presents
theoreticalstudiesonπ-electronrotationsofmolecules,Mgporphyrin,benzeneand
ansa (planar chirality) chiral aromatic molecules, which are induced by ultrashort
laser pulses. Chapter 7 shows real-time observation of stilbene cis-trans coherent
isomerizationincondensedphases,whichisoneofthetypicalexamplesofphoto-
chemicalreactions.Resultsofexperimentsonlasercontrolofretinalisomerization
in rhodopsin are also shown. Chapter 8 presents applications of quantum control
theorytomolecularchirality.Severalmethodssuchaspump-dumpcontrol,stimu-
latedRamanadiabaticpassage,andquantumcontrolmethodsareapplied.Molecular
chiralityisanessentialpropertyofbiomolecules.Thedevelopmentofnewmethods
foridentificationandtransformationofchiralityisachallengingsubject.
Wewouldliketothankourcolleagues,co-researchesandfriends:Profs.S.Aono,
A.D.Bandrauk,S.L.Chin,P.B.Corkum,W.Domcke,L.González,I.V.Hertel,M.
Kanno, S. Koseki, Z. Lan , F. H. M. Faisal, G. Gerber, S. H. Lin, R. J. Gordon,
M. Hayashi, K. Hoki, T. Kato, N. Kobayashi, H. Kono, D. Kröener, Y. Manz,
D. Mathur, K. Miyazaki, H. Nakamura, Y. Nomura, T. Nguyen-Dan, Y. Ohta,
Y. Ohtsuki, R. Sahnoun, N. Shimakura, M. Sugawara, M. Tanaka, K. Terarishi,
H. Umeda, K.Yamanouchi, K.Yamashita andY.Yan, Drs. I. Kawata, K. Nakai,
Y.SatoandM.Yamaki,Ms.M.Abe,andK.Haruyama,A.Kita,M.Muramatsuand
April7,2011 16:3 9.75inx6.5in b1101-fm ElectronicandNuclearDynamicsinMolecularSystems
Preface vii
K. Nakagami.YF would like to express special thanks to Prof. H. Kono and Prof.
Y.Ohtsukiwhowerepartnersincarryingouthard-timeresearchprojectsatTohoku
University,SendaiJapan.ProfessorH.Konohasmadeasubstantialcontributionto
thedevelopmentofelectronicquantumdynamicswithDr.I.Kawata.
PartsofthismonographwerecompletedwhileYFwasaresearchfellowatthe
InstituteofAtomicandMolecularScienceswithsupportbyAcademicSimicaand
National Science Council of Taiwan, to which Prof. Lin kindly invited him. YF
appreciatesthewarmhospitalityofM.Hayashi,ProfessorofCenterforCondensed
MatterPhysics.
The staff at World Scientific Publishing were exceedingly helpful, including
EditorsV.K.SanjeedandC.Xingliang.
ThismonographisdedicatedtothelateProfessorsT.NakajimaandT.Abe,who
providedsupportandencouragementattheinitialstagesofYF’sresearchprojects.
The authors acknowledge financial support from JSPS (Japan Society for the
PromotionofScience)andMEXT(MinistryofEducation,Culture,Sports,Science,
andTechnology).

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Contents
Preface v
1. BasicConceptsandFundamentalDynamics 1
1. Wavepacket . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. AdiabaticandNonadiabaticTreatments . . . . . . . . . . . . . . 3
3. QuantumControlbyPulseShaping . . . . . . . . . . . . . . . . 4
4. Multiphotonvs.TunnelingIonization . . . . . . . . . . . . . . . 6
5. High-OrderHarmonicGeneration(HHG) . . . . . . . . . . . . . 7
6. RescatteringofElectrons . . . . . . . . . . . . . . . . . . . . . . 10
7. Above-ThresholdIonization(ATI) . . . . . . . . . . . . . . . . . 11
8. Above-ThresholdDissociation(ATD) . . . . . . . . . . . . . . . 12
9. CoulombExplosion . . . . . . . . . . . . . . . . . . . . . . . . . 13
10. AlignmentandOrientation . . . . . . . . . . . . . . . . . . . . . 15
11. MolecularChirality . . . . . . . . . . . . . . . . . . . . . . . . . 17
12. MolecularADKTheoryforTunnelingIonizationRate. . . . . . . 19
13. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2. ExperimentalSetupsandMethods 25
1. Laser-InducedCoulombExplosionImaging . . . . . . . . . . . . 25
2. High-OrderHarmonicGeneration . . . . . . . . . . . . . . . . . 26
3. MolecularOrientationandItsObservation . . . . . . . . . . . . . 28
3.1 1Dmolecularorientation . . . . . . . . . . . . . . . . . . 28
3.2 3Dmolecularorientation . . . . . . . . . . . . . . . . . . 30
3. TheoreticalTreatmentsofWavepackets 35
1. GenerationofWavepacketandItsPropagation . . . . . . . . . . . 35
2. NumericalMethodsforWavepacketPropagation . . . . . . . . . 39
ix